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Qing Yun Li ; Leigh Anna Hunt ; Kalpani Hirunika Wijesinghe , et al. Adv. Energy Mater.,2023,13(2):2203102. DOI: 10.1002/aenm.202203102
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Abstract: Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long-lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6-dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady-state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 μs. The long-lived excited state photosensitizer is well-suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water-soluble photosensitizer.
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CAS No. : | 22385-77-9 | MDL No. : | MFCD00796945 |
Formula : | C14H21Br | Boiling Point : | No data available |
Linear Structure Formula : | ((CH3)3C)2C6H3Br | InChI Key : | BUOWTUULDKULFI-UHFFFAOYSA-N |
M.W : | 269.22 | Pubchem ID : | 620136 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H332-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Bromo-3,5-di-tert-butylbenzene (1.3 g, 5 mmole) was dissolved in THF (20 mL), to this solution was slowly added n-BuLi (1.6 M, 3.3 mL) at -78° C., the reaction was stirred at this temperature for 30 min, trimethyl borate (0.75 g, 7.5 mmole) was added all at once, stir over night while the reaction was allowed to slowly warm up to room temperature. Hydrochloric acid (6N, 5 mL) was added and stirred for 3 hrs at room temperature. Water (200 mL) was added, and the precipitate was collected, washed with water (10 mL.x.3), dried under vacuum to give titled compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With magnesium bromide diethyl etherate; In pentane; | 2-(3,5-Di-t-butylphenyl)indene (Ligand D) 1-Bromo-3.5-di-t-butylbenzene (47.2g, 0.175 mol) was dissolved in ether (500 mL) and cooled to -70C. t-Butyllithium (200 mL of 1.7 M solution in pentane, 0.34 mol) was added at -70C over a two-hour period. The solution was allowed to warm to room temperature slowly. Magnesium bromide etherate (46.5g. 0.18 mol) was added and the slurry was stirred for one hour. The mixture was then cooled to 5C and <strong>[10485-09-3]2-bromoindene</strong> (34.2 g, 0.18 mol) was added. The mixture was warmed to room temperature and then refluxed for three hours. The solution was cooled to room temperature and the reaction was quenched carefully with water. The layers were separated and the organics washed with salt brine and dried over magnesium sulfate. The solvents were evaporated and the product was distilled twice and recrystallized from hexane to give 37.1 g of product (70% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | 1-Bromo-3,5-di-t-butylbenzene and 40 mL of tetrahydrofuran were put in a 100-mL glass reactor, and cooled to ?70° C. in a dry ice-heptane bath. 16.4 mL (40.9 mmol) of n-butyllithium-n-hexane solution (2.5 mol/L) was dropwise added thereto, and stirred for 30 minutes. Subsequently at ?78° C., 4.25 g (40.9 mmol) of trimethyl borate was added and stirred for 2 hours, and further stirred at room temperature for 12 hours. An aqueous 1 M hydrogen chloride solution was added to the reaction liquid until the pH of the liquid could reach 3, then transferred into a separatory funnel, extracted three times with t-butyl methyl ether, and dried with sodium sulfate. Sodium sulfate was filtered away, the solvent was evaporated under reduced pressure, and the resultant crude product was purified through silica gel column chromatography (developing solvent, petroleum ether/ethyl acetate=20/1) to give 8.00 g (yield 91percent) of 3,5-di-t-butylphenylboronic acid as a pale yellow solid | |
With hydrogenchloride; In tetrahydrofuran; diethyl ether; water; | Synthesis of (3,5-di-tert-butylphenyl)boronic acid.10.0 g of 1-Bromo-3,5-di-tert-butylbenzene (37.1 mmol) in 20 ml THF was added dropwise to a suspension of 1.26 g Mg turnings (51.9 mmol) in 30 ml THF.After complete addition the mixture was stirred at reflux for 2.5 h.Subsequently the warm Grignard solution was transferred via canula into a dropping funnel and added dropwise to a solution of 5.77 g trimethyl borate (55.6 mmol) in 100 mL Et2O.During the addition the temperature was kept below - 60 °C.After complete addition the mixture was warmed to room temperature and stirred over night.The reaction was quenched by adding 55.8 ml H2O and 5.6 mL conc. HCl.The organic phase was separated and the aqueous phase was extracted several times with Et2O.The combined organic phases were washed with saturated sodium chloride solution and dried over sodium sulfate.Evaporation of the solvent gave a white solid.Yield 7.59 g (88 percent).The boronic acid was obtained as a mixture of monomers and oligomers and used without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | A solution of 2,2,6,6-tetramethylpiperidine (2.0 mL, 12 mmol) in THF (12 mL) was treated with n-BuLi (7.5mL, 1.60 M in hexane, 12 mmol) at 0 C. After stirring for 1 h at 0 C the solution wasadded to a solution of <strong>[1273-73-0]bromoferrocene</strong> (1.32 g, 5.00 mmol) in THF (10 mL) at -78 C.After stirring for 30 min at -78 C and 3 h at -30 C the reaction mixture wastransferred to a suspension of ZnCl2 (1.36 g, 10.0 mmol) in THF (10 mL) at -78 C.Stirring was continued at -78 C for 30 min before the mixture was warmed to roomtemperature, where stirring was maintained for 30 min. To the resulting solution wasadded a solution of 1-bromo-3,5-di-t-butylbenzene (1.48 g, 5.50 mmol) and [Pd(PPh3)4](0.29 g, 0.25 mmol) in THF (10 mL). The reaction mixture was heated to 60 C for 10hours, before the reaction was quenched with a saturated aqueous ammonium chloridesolution. The reaction mixture was extracted with hexane and the combined organicphases were washed with water and dried over MgSO4. After filtration, the filtrate wasevaporated to dryness under reduced pressure and the obtained residue was purified bycolumn chromatography on silica gel (hexane) to give compound 3 (2.01 g, 4.43 mmol,89%). 3: orange solid; m.p. 87-89 C; 1H NMR (300 MHz, CDCl3) δ 1.37 (s, 18H), 4.17(s, 5H), 4.22 (t, J = 2.6 Hz, 1H), 4.43 (dd, J = 2.6, 1.4 Hz), 4.54 (dd, J = 2.6, 1.4 Hz),7.33 (t, J = 1.8 Hz, 1H), 7.55 (d, J = 1.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 31.6 (q),34.8 (q), 66.3 (d), 67.5 (d), 71.0 (d), 72.0 (d), 78.3 (s), 87.7 (s), 120.8 (d), 123.9 (d),135.2 (s), 149.8 (s). Anal. Calcd for C24H29BrFe: C, 63.60; H, 6.45%. Found: C, 63.84;H, 6.48%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1-bromo-3,5-di-tert-butylbenzene (20.1 g, 77.4 mmol) was dissolved in THF (400 mL) underAr at ?78 °C. 1.64 M solution of n?BuLi in n-Hexane (100 mL, 164 mmol) was slowly added.After the solution was stirred at ?78 °C for 1.5 h, triisopropyl borate (44.0 mL, 189 mmol)dissolved in THF (60.0 mL) was immediately added. The solution was stirred overnight atroom temperature. Et2O and 10percent HCl aq. were added to the solution, the organic layer wasseparated and dried over MgSO4, then filtered. The solvent was removed by evaporation toyield 2 as a white solid (21.2 g, crude). And 2, 1,3,5-tribromobenzene (48.7 g, 155 mmol),Pd(PPh3)4 (1.79 g, 1.55 mmol), Na2CO3 (16.4 g, 155 mmol) were dissolved in toluene (678 mL),EtOH (255 mL) and H2O (110 mL) under Ar. The solution was stirred 22 h at 100 °C. Et2O andCH2Cl2 was added to the solution and the organic layer was separated and dried over MgSO4,and then filtered. The solvent was removed by evaporation, and the residue was purified by column chromatography on silica gel (eluent : n-Hexane) to yield 3 as a white solid (16.8 g,39.6 mmol, 2 steps 63 percent). |
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